, Volume 26, Issue 18, pp 9687–9708 | Cite as

Overcoming biomass recalcitrance to enhance platform chemical production from soft wood by organosolvolysis coupled with fast pyrolysis

  • Xingwei Yang
  • Anqing ZhengEmail author
  • Zengli ZhaoEmail author
  • Shengpeng Xia
  • Yuyang Fan
  • Chaojin Zhou
  • Fengzhu Cao
  • Liqun Jiang
  • Guoqiang Wei
  • Zhen Huang
  • Haibin Li
Original Research


Softwood is an abundantly available lignocelloluse feedstock which can be converted into chemical and liquid fuels via sugar-based platform molecules. However, cost-effective release of pyrolytic sugars from softwood is considerably hindered by the biomass recalcitrance related to its compositions and structures as well as the catalytic effect of alkali and alkaline earth metals. In order to address these challenges, a novel biorefinery based on H2SO4 assisted organosolvolysis of softwood (e.g. pine wood) in high boiling organic solvents coupled with subsequent fast pyrolysis is proposed. The experimental results demonstrated that H2SO4 assisted organosolvolysis could effectively deconstruct pine wood into pentose, organosolv lignin, cellulose-rich fraction, and simutaneously transfer alkali and alkaline earth metals to solutions, thus improving the yields of platform chemcials (levoglucosan and phenols) in subsequent fast pyrolysis. Moreover, different high boiling solvents showed obviously distinct performance for the deconstruction of pine wood and removal of alkali and alkaline earth metals, thus resulting in different yields of platform chemcials in the subsequent fast pyrolysis. The rank order of these solvents which are beneficial for improving the yield of pyrolytic sugars from pine wood was ethylene glycol > glycerin + ethylene glycol (mass ratio of 1:1) > glycerin > γ-valerolactone. The yield of levoglucosan increased drastically from 3.53 wt% of raw pine wood to 27.19 wt% of cellulose-rich fraction pretreated by ethylene glycol with 1 wt% H2SO4. It was found that the yield of levoglucosan from fast pyrolysis of feedstocks was subjecetd to the mutual effect of normalized total alkali and alkaline earth metals’ valencies and severity of delignification. These findings help to provide a simple and efficient process to selective production of platform chemicals from highly recalcitrant biomass.


Soft wood Biomass recalcitrance Platform chemicals Organosolvolysis Fast pyrolysis 



The authors acknowledge the National Natural Science Foundation of China (Grants 51876208, 51776209, 51606204), Major International (Regional) Joint Research Project of the National Science Foundation of China (Grant 51661145011), National Key R&D Program of China (Grant 2017YFE0124200), Science and Technology Planning Project of Guangdong Province, China (Grants 2014B020216004, 2015A020215024), Youth Innovation Promotion Association, CAS (2018383), and Pearl River S&T Nova Program of Guangzhou (Grant 201806010061) for their financial supports of this work. We would also like to express our sincere gratitude to the staffs from analysis and testing center attached to Guangzhou Institute of Energy Conversion for their assistance in characterization and testing.


  1. Atienza-Martinez M, Fonts I, Lazaro L, Ceamanos J, Gea G (2015) Fast pyrolysis of torrefied sewage sludge in a fluidized bed reactor. Chem Eng J 259:467–480. CrossRefGoogle Scholar
  2. Boeriu CG, Bravo D, Gosselink RJA, van Dam JEG (2004) Characterisation of structure-dependent functional properties of lignin with infrared spectroscopy Ind Crop. Prod 20:205–218. CrossRefGoogle Scholar
  3. Bridgwater AV (2003) Renewable fuels and chemicals by thermal processing of biomass. Chem Eng J 91:87–102. CrossRefGoogle Scholar
  4. Casas A, Alonso MV, Oliet M, Rojo E, Rodriguez F (2012) FTIR analysis of lignin regenerated from Pinus radiata and Eucalyptus globulus woods dissolved in imidazolium-based ionic liquids. J Chem Technol Biot 87:472–480. CrossRefGoogle Scholar
  5. Chen HM, Zhao J, Hu TH, Zhao XB, Liu DH (2015) A comparison of several organosolv pretreatments for improving the enzymatic hydrolysis of wheat straw: substrate digestibility, fermentability and structural features. Appl Energy 150:224–232. CrossRefGoogle Scholar
  6. DeMartini JD, Pattathil S, Miller JS, Li HJ, Hahn MG, Wyman CE (2013) Investigating plant cell wall components that affect biomass recalcitrance in poplar and switchgrass Energ. Environ Sci 6:898–909. CrossRefGoogle Scholar
  7. Faix O (1991) Classification of lignins from different botanical origins by FT-IR spectroscopy. Holzforschung 45:21–27. CrossRefGoogle Scholar
  8. Fan YY, Zhang DY, Zheng AQ, Zhao ZL, Li HB, Yang TH (2019) Selective production of anhydrosugars and furfural from fast pyrolysis of corncobs using sulfuric acid as an inhibitor and catalyst. Chem Eng J 358:743–751. CrossRefGoogle Scholar
  9. French ADJC (2014) Idealized powder diffraction patterns for cellulose polymorphs 21:885–896Google Scholar
  10. Garcia-Perez M et al (2008) Fast pyrolysis of oil mallee woody biomass: effect of temperature on the yield and quality of pyrolysis products. Ind Eng Chem Res 47:1846–1854. CrossRefGoogle Scholar
  11. Ghasemi M, Tsianou M, Alexandridis P (2018) Population ensemble modeling of biomass dissolution. Chem Eng J 350:37–48. CrossRefGoogle Scholar
  12. Gschwend FJV, Chambon CL, Biedka M, Brandt-Talbot A, Fennell PS, Hallett JP (2019) Quantitative glucose release from softwood after pretreatment with low-cost ionic liquids. Green Chem 21:692–703. CrossRefGoogle Scholar
  13. Hassan E, Abou-Yousef H, Steele P (2013) Increasing the efficiency of fast pyrolysis process through sugar yield maximization and separation from aqueous fraction bio-oil. Fuel Process Technol 110:65–72. CrossRefGoogle Scholar
  14. Himmel ME (2007) Biomass recalcitrance: engineering plants and enzymes for biofuels production (vol 315, pg 804, 2007). Science 316:982Google Scholar
  15. Himmel ME, Ding SY, Johnson DK, Adney WS, Nimlos MR, Brady JW, Foust TD (2007) Biomass recalcitrance: engineering plants and enzymes for biofuels production. Science 315:804–807. CrossRefGoogle Scholar
  16. Hoekstra E, Van Swaaij WPM, Kersten SRA, Hogendoorn KJA (2012a) Fast pyrolysis in a novel wire-mesh reactor: decomposition of pine wood and model compounds. Chem Eng J 187:172–184. CrossRefGoogle Scholar
  17. Hoekstra E, van Swaaij WPM, Kersten SRA, Hogendoorn KJA (2012b) Fast pyrolysis in a novel wire-mesh reactor: design and initial results. Chem Eng J 191:45–58. CrossRefGoogle Scholar
  18. Hosoya T, Sakaki S (2013) Levoglucosan formation from crystalline cellulose: importance of a hydrogen bonding network in the reaction. Chemsuschem 6:2356–2368. CrossRefPubMedGoogle Scholar
  19. Jiang LQ, Zheng AQ, Zhao ZL, He F, Li HB, Liu WG (2015) Obtaining fermentable sugars by dilute acid hydrolysis of hemicellulose and fast pyrolysis of cellulose. Bioresource Technol 182:364–367. CrossRefGoogle Scholar
  20. Jiang LQ, Fang Z, Zhao ZL, Zheng AQ, Wang XB, Li HB (2019) Levoglucosan and its hydrolysates via fast pyrolysis of lignocellulose for microbial biofuels: a state-of-the-art review. Renew Sust Energy Rev 105:215–229. CrossRefGoogle Scholar
  21. Kan T, Strezov V, Evans TJ (2016) Lignocellulosic biomass pyrolysis: a review of product properties and effects of pyrolysis parameters. Renew Sustain Energy Rev 57:1126–1140. CrossRefGoogle Scholar
  22. Kubo S, Kadla JF (2005) Hydrogen bonding in lignin: a Fourier transform infrared model compound study. Biomacromolecules 6:2815–2821. CrossRefPubMedGoogle Scholar
  23. Lee JM, Jameel H, Venditti RA (2010) A comparison of the autohydrolysis and ammonia fiber explosion (AFEX) pretreatments on the subsequent enzymatic hydrolysis of coastal Bermuda grass. Bioresource Technol 101:5449–5458. CrossRefGoogle Scholar
  24. Li M, Tu MB, Cao DX, Bass P, Adhikari S (2013) Distinct roles of residual xylan and lignin in limiting enzymatic hydrolysis of organosolv pretreated loblolly pine and sweetgum. J Agric Food Chem 61:646–654. CrossRefPubMedGoogle Scholar
  25. Lian JN, Chen SL, Zhou SA, Wang ZH, O’Fallon J, Li CZ, Garcia-Perez M (2010) Separation, hydrolysis and fermentation of pyrolytic sugars to produce ethanol and lipids. Bioresource Technol 101:9688–9699. CrossRefGoogle Scholar
  26. Linde M, Jakobsson E, Galbe M, Zacchi G (2008) Steam pretreatment of dilute H2SO4-impregnated wheat straw and SSF with low yeast and enzyme loadings for bioethanol production. Biomass Bioenergy 32:326–332. CrossRefGoogle Scholar
  27. Liu JA, Takada R, Karita S, Watanabe T, Honda Y, Watanabe T (2010) Microwave-assisted pretreatment of recalcitrant softwood in aqueous glycerol. Bioresource Technol 101:9355–9360. CrossRefGoogle Scholar
  28. Lu Q, Li WZ, Zhu XF (2009) Overview of fuel properties of biomass fast pyrolysis oils. Energy Convers Manag 50:1376–1383. CrossRefGoogle Scholar
  29. Mahadevan R, Adhikari S, Shakya R, Wang K, Dayton D, Lehrich M, Taylor SE (2016) Effect of alkali and alkaline earth metals on in-situ catalytic fast pyrolysis of lignocellulosic biomass: a microreactor study. Energy Fuel 30:3045–3056. CrossRefGoogle Scholar
  30. Maqbool W, Hobson P, Dunn K, Doherty W (2017) Supercritical carbon dioxide separation of carboxylic acids and phenolics from bio-oil of lignocellulosic origin: understanding bio-oil compositions, compound solubilities, and their fractionation. Ind Eng Chem Res 56:3129–3144. CrossRefGoogle Scholar
  31. Mcdonough TJ (1993) The chemistry of organosolv delignification. Tappi J 76:186–193Google Scholar
  32. Pandey KK, Pitman AJ (2003) FTIR studies of the changes in wood chemistry following decay by brown-rot and white-rot fungi. Int Biodeter Biodegr 52:151–160. CrossRefGoogle Scholar
  33. Patwardhan PR, Satrio JA, Brown RC, Shanks BH (2010) Influence of inorganic salts on the primary pyrolysis products of cellulose. Bioresour Technol 101:4646–4655. CrossRefPubMedGoogle Scholar
  34. Poletto M, Zattera AJ, Forte MMC, Santana RMC (2012) Thermal decomposition of wood: influence of wood components and cellulose crystallite size. Bioresource Technol 109:148–153. CrossRefGoogle Scholar
  35. Segal L, Creely JJ, Martin AE, Conrad CM (1959) An empirical method for estimating the degree of crystallinity of native cellulose using the X-ray diffractometer. Text Res J 29:786–794. CrossRefGoogle Scholar
  36. Sharma RK, Wooten JB, Baliga VL, Lin XH, Chan WG, Hajaligol MR (2004) Characterization of chars from pyrolysis of lignin. Fuel 83:1469–1482. CrossRefGoogle Scholar
  37. Shen D, Jin W, Hu J, Xiao R, Luo K (2015) An overview on fast pyrolysis of the main constituents in lignocellulosic biomass to valued-added chemicals: structures, pathways and interactions. Renew Sustain Energy Rev 51:761–774. CrossRefGoogle Scholar
  38. Smit A, Huijgen W (2017) Effective fractionation of lignocellulose in herbaceous biomass and hardwood using a mild acetone organosolv process. Green Chem 19:5505–5514. CrossRefGoogle Scholar
  39. Wang SR, Guo XJ, Wang KG, Luo ZY (2011) Influence of the interaction of components on the pyrolysis behavior of biomass. Anal Appl Pyrol 91:183–189. CrossRefGoogle Scholar
  40. Wang SR, Wang YR, Cai QJ, Wang XY, Jin H, Luo ZY (2014) Multi-step separation of monophenols and pyrolytic lignins from the water-insoluble phase of bio-oil. Sep Purif Technol 122:248–255. CrossRefGoogle Scholar
  41. Wang S, Dai G, Yang H, Luo Z (2017) Lignocellulosic biomass pyrolysis mechanism: a state-of-the-art review. Prog Energy Combust Sci 62:33–86. CrossRefGoogle Scholar
  42. Wu SL, Shen DK, Hu J, Zhang HY, Xiao R (2016) Cellulose-lignin interactions during fast pyrolysis with different temperatures and mixing methods. Biomass Bioenerg 90:209–217. CrossRefGoogle Scholar
  43. Yildiz G, Ronsse F, Venderbosch R, van Duren R, Kersten SRA, Prins W (2015) Effect of biomass ash in catalytic fast pyrolysis of pine wood. Appl Catal B-Environ 168:203–211. CrossRefGoogle Scholar
  44. Yu Y, Liu DW, Wu HW (2014) Formation and characteristics of reaction intermediates from the fast pyrolysis of NaCl- and MgCl2-loaded celluloses. Energy Fuel 28:245–253. CrossRefGoogle Scholar
  45. Zhang J, Choi YS, Yoo CG, Kim TH, Brown RC, Shanks BH (2015) Cellulose–hemicellulose and cellulose-lignin interactions during fast pyrolysis. ACS Sustain Chem Eng 3:293–301. CrossRefGoogle Scholar
  46. Zhang K, Pei ZJ, Wang DH (2016) Organic solvent pretreatment of lignocellulosic biomass for biofuels and biochemicals: a review. Bioresource Technol 199:21–33. CrossRefGoogle Scholar
  47. Zhao XB, Liu DH (2012) Fractionating pretreatment of sugarcane bagasse by aqueous formic acid with direct recycle of spent liquor to increase cellulose digestibility-the Formiline process. Bioresource Technol 117:25–32. CrossRefGoogle Scholar
  48. Zhao XB, Cheng KK, Liu DH (2009) Organosolv pretreatment of lignocellulosic biomass for enzymatic hydrolysis. Appl Microbiol Biot 82:815–827. CrossRefGoogle Scholar
  49. Zhao XB, Zhang LH, Liu DH (2012a) Biomass recalcitrance. Part I: the chemical compositions and physical structures affecting the enzymatic hydrolysis of lignocellulose. Biofuel Bioprod Bior 6:465–482. CrossRefGoogle Scholar
  50. Zhao XB, Zhang LH, Liu DH (2012b) Biomass recalcitrance. Part II: Fundamentals of different pre-treatments to increase the enzymatic digestibility of lignocellulose. Biofuel Bioprod Bior 6:561–579. CrossRefGoogle Scholar
  51. Zheng AQ et al (2015) Overcoming biomass recalcitrance for enhancing sugar production from fast pyrolysis of biomass by microwave pretreatment in glycerol. Green Chem 17:1167–1175. CrossRefGoogle Scholar
  52. Zheng AQ et al (2016a) Effect of hydrothermal treatment on chemical structure and pyrolysis behavior of eucalyptus wood. Energy Fuels 30:3057–3065. CrossRefGoogle Scholar
  53. Zheng AQ et al (2016b) Bridging the gap between pyrolysis and fermentation: improving anhydrosugar production from fast pyrolysis of agriculture and forest residues by microwave-assisted organosolv pretreatment. ACS Sustain Chem Eng 4:5033–5040. CrossRefGoogle Scholar
  54. Zheng AQ et al (2017) Toward fast pyrolysis-based biorefinery: selective production of platform chemicals from biomass by organosolv fractionation coupled with fast pyrolysis. ACS Sustain Chem Eng 5:6507–6516. CrossRefGoogle Scholar
  55. Zheng AQ et al (2018) Effect of microwave-assisted organosolv fractionation on the chemical structure and decoupling pyrolysis behaviors of waste biomass. J Anal Appl Pyrol 131:120–127. CrossRefGoogle Scholar
  56. Zhou ZY, Lei FH, Li PF, Jiang JX (2018) Lignocellulosic biomass to biofuels and biochemicals: a comprehensive review with a focus on ethanol organosolv pretreatment technology. Biotechnol Bioeng 115:2683–2702. CrossRefPubMedGoogle Scholar

Copyright information

© Springer Nature B.V. 2019

Authors and Affiliations

  1. 1.Guangzhou Institute of Energy ConversionChinese Academy of SciencesGuangzhouPeople’s Republic of China
  2. 2.CAS Key Laboratory of Renewable EnergyGuangzhouPeople’s Republic of China
  3. 3.Guangdong Provincial Key Laboratory of New and Renewable Energy Research and DevelopmentGuangzhouPeople’s Republic of China
  4. 4.University of Chinese Academy of SciencesBeijingPeople’s Republic of China
  5. 5.South China University of TechnologyGuangzhouPeople’s Republic of China

Personalised recommendations